The Parisian club has now secured the prestigious trophy on fourteen separate times.
Paris Saint-Germain needed a dramatic leveler followed by a perfect spot-kick decider to get past Marseille in the Gulf and secure a record-extending fourth consecutive French Super Cup title.
The European champions appeared to be sailing towards a straightforward win in the showdown featuring the French league winners and the Coupe de France winners after Ousmane Dembele found the scoring in the opening stages.
However, the southern French side struck two times late to seize a shock advantage. Initially, Mason Greenwood scored from the penalty spot, before Willian Pacho inadvertently directed the ball into his own net for an own goal.
In a remarkable turn of events, Goncalo Ramos grabbed a crucial equaliser in the final moments to send the match into a deciding shootout. PSG goalkeeper Chevalier then stood as the key figure, stopping crucial attempts from O'Riley and Traore.
From the spot, Ramos, Vitinha, the full-back, and Desire Doue all converted with composure for PSG to seal a convincing penalty win.
Now 14-time winners Paris Saint-Germain, who faced last season's Ligue 1 second-placed team Olympique de Marseille after completing a league and cup double, have now won this competition for the twelfth time in the last thirteen seasons.
